Preparation of N Modified Ni2P-Nx/SiO2 Catalysts and Hydrodeoxygenation Performance of m-Cresol

doi:10.6023/A24070217

Abstract

The gradual depletion of fossil fuels and increasing environmental pollution problems inspire researchers to seek renewable and clean energy. Lignocellulosic biomass is deemed to be a sustainable and promising resource to produce chemicals and fuels due to its abundant existence in nature. Hydrodeoxygenation (HDO) of phenolic compounds in bio-fuel is a promising technology to convert biomass materials to value-added chemicals and fuels. However, the development of highly efficient catalysts remains a great challenge. In this work, a series of N modified Ni₂P-N_x/SiO₂ catalysts were prepared by impregnation method. The structure of the catalysts was characterized by X-ray diffraction (XRD), N₂ physical adsorption desorption (BET), H₂ temperature programmed reduction (H₂-TPR), NH₃ temperature programmed desorption (NH₃-TPD), pyridine infrared (Py-FTIR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and the influence of Ni/N molar ratio on the physicochemical properties of the catalysts was systematically investigated. Using m-cresol as a model compound, the effects of Ni/N molar ratio, reaction temperature, reaction time, and reaction pressure on the HDO performance were studied. It was found that the appropriate introduction of N element can promote the formation of smaller active particles, improve the dispersion of active components, thus enhancing the catalytic activity. The Ni₂P-N_1.0/SiO₂ catalyst with a Ni/N ratio of 1.0 exhibited the best HDO activity. Under the conditions of 250 ℃, 3 MPa, and 1 h, m-cresol conversion reached 93.2%, and the selectivity of the target product methylcyclohexane (MCH) reached 94.2%. Based on the product distribution, it can be inferred HDO of m-cresol over Ni₂P-N_x/SiO₂ catalyst proceeded mainly via hydrogenation-deoxygenation (HYD) pathway. Furthermore, this series of catalysts also displayed excellent recyclability, m-cresol conversion, as well as the selectivity towards MCH did not decrease obviously even after 5 successive cycles. We believe that this strategy can provide a simple and repeatable route to synthesize high-performance HDO catalysts.

Key words: N modified, Ni₂P-N_x/SiO₂ catalyst, m-cresol, hydrodeoxygenation, methylcyclohexane

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Shuai Wang, Hua Song. Preparation of N Modified Ni₂P-N_x/SiO₂ Catalysts and Hydrodeoxygenation Performance of m-Cresol[J]. Acta Chimica Sinica, 2024, 82(9): 979-986.

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Fig. & Tab. 17

Figure 1. XRD spectra of Ni2P-Nx/SiO2 catalysts with different Ni/N ratios

Figure 2. N2 adsorption-desorption isotherms (a) and pore size distribution (b) for Ni2P-Nx/SiO2 catalysts

Sample	S_BET/(m²•g⁻¹)	Pore volume/(cm³•g⁻¹)	Pore size/nm	Ni loading^a/%	Surface N content^b	Surface P content^c
Ni₂P/SiO₂	381.2	0.776	7.9	8.79	—	2.68
Ni₂P-N_0.25/SiO₂	321.5	0.636	7.7	—	—	—
Ni₂P-N_0.5/SiO₂	331.2	0.653	7.5	—	—	—
Ni₂P-N_1.0/SiO₂	359.5	0.665	7.4	8.63	1.34	2.54
Ni₂P-N_1.5/SiO₂	354.4	0.650	7.7	—	—	—
Ni₂P-N_2.0/SiO₂	350.5	0.637	7.3	—	—	—

Table 1. Structural properties of Ni2P-Nx/SiO2 catalysts

Figure 3. H2-TPR spectra of the precursors

Figure 4. NH3-TPD spectra of the Ni2P-Nx/SiO2 catalysts

Figure 5. Py-FTIR spectra of the Ni2P-Nx/SiO2 catalysts

Sample	Total acid/ (μmol•g⁻¹)	Acid sites distribution^a/(μmol•g⁻¹)
Sample	Total acid/ (μmol•g⁻¹)	Brönsted acid	Lewis acid	B/L
Ni₂P/SiO₂	373.6	48.8	324.8	0.15
Ni₂P-N_0.5/SiO₂	271.4	31.3	240.0	0.14
Ni₂P-N_1.0/SiO₂	298.3	32.2	266.1	0.12
Ni₂P-N_1.5/SiO₂	230.2	22.9	207.3	0.11

Table 2. The acidity of the Ni2P-Nx/SiO2 catalysts

Figure 6. TEM images of Ni2P-N1.0/SiO2 (a, b) and Ni2P/SiO2 (c) catalysts

Figure 7. XPS spectra of the Ni2P-N1.0/SiO2 catalyst

Figure 8. Effect of Ni/N molar ratio on HDO performance of cresol over Ni2P-Nx/SiO2 catalysts

Figure 9. Effect of reaction temperature on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

Figure 10. Effect of reaction time on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

Figure 11. Effect of reaction pressure on HDO performance of cresol over Ni2P-N1.0/SiO2 catalyst

Catalyst	t/h	T/℃	p/MPa	Con./%	O-free product sel/%	Ref.
Ni₂P-N_1.0/SiO₂	1	250	3	93.2	94.2	This work
MoS₂	5	250	4	48.9	96.2	[23]
FeS₂	5	250	4	1.1	90.6	[23]
FeS-MoS₂-0.3	5	250	4	98.3	98.4	[23]
Mo-S	5	275	4	33.3	85.9	[24]
Co-Mo-S	5	275	4	76.4	98.3	[24]
Co-MoS₂	4	300	4	33.1	95.6	[25]

Table 3. Comparison of m-cresol HDO performance over Ni2P-N1.0/SiO2 with reported metal catalysts

Figure 12. Stability of the Ni2P-N1.0/SiO2 catalyst

底物	目标产物	转化率/%	选择性/%
苯酚	环己烷	97.8	96.4
对甲酚	甲基环己烷	93.5	95.3
邻甲酚	甲基环己烷	91.9	93.4
愈创木酚	环己烷	87.6	92.9

Table 4. Substrates extension of Ni2P-N1.0/SiO2 catalyst

Figure 13. Reaction pathway for HDO of cresol over Ni2P-N1.0/SiO2 catalyst

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氮修饰Ni₂P-N_x/SiO₂催化剂设计合成及间甲酚加氢脱氧性能研究

Preparation of N Modified Ni₂P-N_x/SiO₂ Catalysts and Hydrodeoxygenation Performance of m-Cresol

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氮修饰Ni2P-Nx/SiO2催化剂设计合成及间甲酚加氢脱氧性能研究